HUT68690A - Acid microemulsion composition - Google Patents

Abstract

An acidic thickened microemulsion composition which contains alpha hydroxy aliphatic acids and is effective in removing soap scum.

Description

The present invention relates to an acidic microemulsion composition. The present invention relates to a composition for cleaning hard surfaces such as bathtub, kitchen drain, tile, porcelain, enamel, and the composition can be used to remove soap foam, limescale and grease without damaging the surfaces.

More particularly, the present invention is an acidic microemulsion composition that can be sprayed onto the surface to be cleaned, wiped without conventional rinsing, and remains clean and shiny. The invention also relates to a process for the use of such compositions.

Surface cleaners such as bath cleaners and abrasives have been known for many years. Abrasives typically include soaps, synthetic organic detergents, surfactants, and abrasives. These products can scratch relatively soft surfaces and possibly blur their surface. Often these products do not effectively remove scale (calcium and magnesium carbonate coating) during normal use. Because scale can be removed by chemical reaction with an acidic medium, various acidic cleaners have been prepared and have been found to be successful in various ways. In some cases, the cleaning agent's mistake was that the acid used was too strong and therefore damaged the surface to be cleaned. In other cases, the acidic component of the detergent reacted undesirably with the other components of the product, adversely affecting the detergent or the aroma. Certain • · ·

- 3 detergents required subsequent rinsing to remove unwanted coating remaining on the cleaned surface. Research has shown that these disadvantages can be overcome and thus an improved liquid cleaning composition can be successfully formulated in a stable microemulsion form that effectively removes soap foam, limestone and grease stains from hard surfaces. Such surfaces are, for example, bathroom surfaces and therefore do not require rinsing after use. Such a product is disclosed in U.S. Patent Application No. 120,250, filed November 12, 1987, by Lotch, Blanvalat, and Valenge, entitled Stable Microemulsion Cleanser. Example 3 of this specification describes an acidic, clean, oil-in-water microemulsion successfully used to clean shower tiles to remove build-up of scale and adhering soap foam. Such cleaning was done by applying the detergent to the wall, then wiping it off or after a little rinsing, then allowing the wall to dry to give a shiny surface.

The microemulsion cleaner described in that patent application successfully removes limescale and soap foam from hard surfaces and is easy to apply, but we have found that a mixture of acidic components (succinic acid, glutaric acid and adipic acid) can damage certain hard surfaces that are not acid-resistant. One of these materials is enamel, which is widely used in Europe as a coating for bathtubs, • · • · ·

Hereinafter referred to as European Enamel. It is called zirconium white enamel or zirconium white powder enamel and has the advantage of being resistant to detergents and is therefore suitable for bathtubs, kitchen sinks, shower tiles and bathroom enamels.

However, this enamel is sensitive to acids and is severely damaged by a microemulsion acidic detergent based on the three organic carboxylic acid components mentioned above.

This problem was solved in European Patent 0 336878A2. Here, additional acidic substances are included in the detergent along with organic acids, which, instead of aggravating the problem, help prevent damage to the European enamel surface by organic acids. A mixture of such additional acids, phosphonic and phosphoric acids, surprisingly improves the safety of the aqueous detergent when applied to European enamel surfaces and reduces the detergent cost.

The compositions of the present invention may clean European enamel surfaces as well as any other acid resistant bathtub or other bathroom surface. The product may also be used for various other materials which are particularly sensitive to acidic media, such as marble. Alpha-hydroxy aliphatic acids are used in the compositions of the present invention instead of a mixture of succinic acid, glutaric acid and adipic acid, which has previously been used in an acidic microemulsion. The composition of the present invention employing alpha-hydroxyaliphatic acids is slightly harmful to the European enamel or other acid-sensitive surface such as marble such as

• · * a mixture of succinic acid, glutaric acid and adipic acid. The composition of the invention may also be thickened with xanthan gum, the disclosure of which is disclosed in U.S. Patent Application Serial No. 07 / 950,370.

The composition of the present invention is for an acidic aqueous detergent for baths and other hard surfaces which are acid-resistant or made of zirconium white enamel having a pH of 1 to 4 and detergent removes limescale, soap foam and grease, to damage this surface. The composition comprises an effective amount of at least one synthetic organic fat stain-removing detergent, an amount of C3 -C5 alpha-hydroxyaliphatic acid or acids to remove limescale and soap foam, and an amino alkylene phosphonic acid in an amount sufficient to prevent α- damage to zirconium white enamel surfaces to be cleaned with hydroxy aliphatic acid; and phosphoric acid, an aqueous medium for detergent, a-hydroxy aliphatic acid, phosphoric acid and aminoalkylene phosphonic acid.

The concentrated acidic microemulsion composition of the present invention comprises the following amounts:

a) 1 to 9% by weight of anionic surfactant, for example C14-C17 alkali metal or ammonium sulfonate, C8-C18 alkali metal or ammonium alkyl sulfate, or C8-C18 alkali metal or ammonium ethoxylated alkyl ether sulfate.

b) 0 to 5% by weight of a nonionic surfactant such as 13 C 15 fatty alcohol EO 7: 1 / PO 4: 1.

.1

c) 0-0.7% of a preservative such as an alkali metal benzoate such as sodium benzoate.

d) 0 to 1.0% xanthan gum thickener having a molecular weight of 1,000,000 to 10,000,000, such as Kelzan T, Merek & Co..

e) 0 to 0.3% alkali metal hydroxide;

f) 0 to 1.0% phosphoric acid, preferably 0.05 to 1.0%.

g) 0 to 0.5% aminotrimethylphosphonic acid, preferably 0.01 to 0.3%.

h) 0 - 0.1% dye,

(i) 0 to 2,0% aroma,

j) 2 to 9%, at least one alpha-hydroxy aliphatic acid containing 2 carbon atoms, and

k) residual water, wherein the pH of the composition is 1-4, preferably

2.7 to 3.3 and a Brookfield viscosity of 5 to 1000 eps, preferably 30 to 600 eps at room temperature and # 2 spindle and 50 rpm.

In the compositions of the present invention, the synthetic organic surfactant may be any anionic, nonionic, amphoteric, ampholytic, zwitterionic or cationic detergent or mixture thereof, but it is preferred to use anionic and nonionic detergents and mixtures thereof.

The nonionic surfactant which may be used is the liquid detergent composition according to the invention in an amount of 0-5%, preferably 0.5-

It is present in an amount of 4.5%, more preferably 1-4% by weight, and is particularly advantageous in removing stains.

Water soluble nonionic surfactants are commercially available

I

7 are well known in the art, including primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkyl phenol ethoxylates and ethylene oxide, propylene oxide, condensates with primary alkanols such as Plurafacs (BASF) and ethylene oxide fatty acid esters condensates such as Tween's (ICI). Nonionic synthetic organic detergents are generally condensation products of organic aliphatic or alkyl aromatic hydrophobic compounds and hydrophilic ethylene oxide groups. Virtually any hydrophobic compound containing a carboxyl, hydroxyl, amido or amino group containing a free hydrogen atom can be condensed with ethylene oxide or a polyhydrate product thereof, polyethylene glycol, and thus forms a water-soluble nonionic detergent. Further, the polyethylene oxide has a hydrophobic and hydrophilic length.

Nonionic detergents include condensation products of higher alcohols, such as alcohols having 8 to 18 carbon atoms, in straight or branched configuration, formed with 5 to 30 moles of ethylene oxide, or, for example, lauryl or myristyl alcohol, 16 moles of ethylene oxide. condensate (EO) or tridecanol with 6 moles of ethylene oxide, myristyl alcohol with 10 moles of ethylene oxide, 1 mole of myristyl alcohol, and a coconut fatty alcohol distillate of ethylene oxide and a fatty alcohol containing 10 to 14 carbon atoms. wherein the condensate comprises either 6 moles of ethylene oxide per mole of alcohol or 9 moles of ethylene oxide per mole of alcohol and 6 to 11 moles of ethylene oxide tallow alcohol ethoxylates.

Of the above nonionic surfactants, Neodol ethoxylates (Shell Co.) are preferred, they are high aliphatic primary alcohols containing from 9 to 15 carbon atoms, for example, 8 moles of C 9-11 alkanol (Neodol 91-8) condensed with ethylene oxide, or 6.5 moles of C 12 -C 13 alkanol (Neodol 23-6.5) condensed with ethylene oxide, 12 moles of C 12 -C 15 alkanol condensed with ethylene oxide (Neodol 25-12), or 13 moles of ethylene oxide condensed 14-15 Carbon alkanol (Neodol 45-13). Such ethoxamers have a hydrophobic lipophilic equilibrium (HLB value) of 8 to 15 and form an emulsion of good olive oil, while ethoxamers of HLB of less than 8 contain less than 5 ethylene oxide groups and are weak emulsifiers or detergents.

Other satisfactory water-soluble alcohol ethylene oxide condensates are 5-8 moles of ethylene oxide condensed products of C8-C18 straight or branched secondary aliphatic alcohols. Commercially available nonionic detergents of the above type include, for example, C 11 -C 15 secondary alkanols condensed with 9 ethylene oxide (Tergitol 15-S-9) or C 11 -C 15 secondary condensed with ethylene oxide (Tergitol 15-S-12). alkanols available from Carbide on the Union.

Other suitable nonionic detergents are condensates of 1 mole alkylphenol having 5 to 30 moles ethylene oxide with straight or branched alkyl groups having 8 to 18 carbon atoms. Alkylphenol ethoxylates include nonylphenol condensates with 9.5 moles of ethylene oxide per mole of nonylphenol, as well as dinonylphenol condensates with 12 moles of ethylene oxide per mole of phenol, and 15 moles of phenol per mole of phenol. dinonylphenol condensates condensed with moles of ethylene oxide; and diisoctylphenol condensates condensed with 15 moles ethylene oxide condensed per mole of phenol. Commercially available nonionic surfactants include, for example, Igepal CO-630, a nonylphenol ethoxylate surfactant sold by GAF Corporation.

Suitable nonionic detergents include condensation products of a water-soluble C8-C20 alkanol with a heterogeneous mixture of ethylene oxide and propylene oxide, wherein the weight ratio of ethylene oxide to propylene oxide is 2.5: 1 to 4: 1, preferably 2, 8: 1 to 3.3: 1, wherein the total amount of ethylene oxide and propylene oxide, including the terminal ethanol or propanol group, is 60-85%, preferably 70-80% by weight. Such detergents are marketed by BASF-Wyandotte, and particularly preferred are condensates of C10-C16 alkanols with ethylene oxide and propylene oxide, wherein the ethylene oxide to propylene oxide weight ratio is 3: 1 and the total alkoxy content is 75%. crowd%.

Condensates of 2 to 30 moles of ethylene oxide sorbitan with mono- and tri-C 10-20 alkanoic acid esters having an HLB of 8 to 15 and useful as a nonionic detergent component in the shampoo described above. These surfactants are well known and are marketed by ICI under the trademark Tween.

Suitable surfactants include, for example, polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.

Other water soluble nonionic detergents marketed under the name Pluronic are less preferred. These compounds are formed by condensing ethylene oxide with a hydrophobic base which is a condensation product of propylene oxide and propylene glycol. The hydrophobic moiety of the molecule has a molecular weight of 950 to 4000, preferably 200 to 2500. Adding polyoxyethylene groups to the hydrophobic moiety increases the solubility of the molecule as a whole so that the surfactant becomes water soluble. The molecular weight of the block polymers ranges from 1000 to 15000 and the polyethylene oxide content can be from 20 to 80% by weight. These surfactants are preferably in liquid form and the corresponding surfactants are available in grades L62 and L64.

The anionic surfactant used in the microemulsion composition comprises 1 to 9, preferably 2 to 8, more preferably 2 to 7% by weight.

The anionic surfactant may be used in the microemulsion detergent of the present invention and is water soluble, such as the triethanolamine salt, and includes

C8-C18 alkyl sulfates, ammonium salts of sodium, potassium, ammonium and ethanol such as lauryl sulfate, myristyl sulfate, etc., as well as C8-C18 ethoxylated alkyl ether sulfates, linear C8-alkylbenzene sulfonates, - C 20 paraffin sulfonates, aolefin sulfonates having from 10 to 24 carbon atoms; C 8 -C 18 alkyl sulfoacetates; C8-C18 alkylsulfosuccinate esters; C 8 -C 18 acyl isethionates; and C 8 -C 18 acyl taurates. The anionic surfactants are preferably water-soluble alkyl sulfates.

The paraffin sulfonates may be monosulfonates or disulfonates, or usually mixtures thereof, obtained by sulfonation of paraffins having from 10 to 20 carbon atoms. Preferred paraffin sulfonates are C12-C18, and more preferably C14-C17. The sulfonate group (s) of paraffin sulfonates are distributed throughout the paraffin chain, see U.S. Patent Nos. 2,503,282, 2,507,088, 3,260,744, U.S. Patent 3,372,188 and German Patent 735,096. Preferably, the content of paraffin sulfonates outside the C14-C17 range is low and can be reduced, as can the content of di- or polysulfonates.

Other suitable sulfonated anionic detergents are well-known lower alkyl mononuclear aromatic sulfonates, such as alkylbenzene sulfonates having a straight or branched chain of 9 to 18, or preferably 9, 10 to 15 or 16 carbon atoms, or alkyl of 8 to 15 carbon atoms. toluenesulfonates. Preferred alkylbenzene sulfonate is linear alkylbenzene sulfonate having a higher 3-phenyl isomer content and well below 50% low 2-phenyl or even lower isomers such as sulfonates wherein the benzene ring alkyl is 3 or higher, for example 4-, 5-,

It is attached at the 6- or 7-position and the content of the isomers to which the benzene ring is attached at the 2- or 1-position is accordingly low. Preferred materials are disclosed in U.S. Patent 3,320,174, especially those wherein the alkyl groups contain from 10 to 13 carbon atoms.

According to the invention

Higher alkyl ether sulfates of formula RO (C 2 H 4 O) are used wherein R is a primary or secondary alkyl group which may be C 10-18, straight or branched, preferably 12-15, more preferably 12-13 carbon atoms. M is an alkali metal or ammonium cation and n is 1-10, preferably 1-6, especially 2 or 3. These detergents are obtained by sulfation of the corresponding ether alcohol and then neutralized with the resulting sulfuric acid esters. Sodium and ammonium salts of ether sulfates are particularly preferred.

The alkyl sulfate anionic detergent compounds according to the invention contain from 6 to 18 carbon atoms in the alkyl group and are represented by the formula R ² SO ₄ M, wherein R ² is a straight or branched C 6 -C 8 alkyl, especially C 8 -C 14 alkyl, and M is an alkali metal or ammonium, especially sodium ion. Straight alkyl groups are preferred.

The active acidic component in acidic emulsions is an alpha-hydroxy aliphatic acid strong enough to lower the pH of the microemulsion to 1-4. A variety of such carboxylic acids can fulfill this function, but those that have been found to be effective in removing soap foam and limescale from bathroom surfaces while not destabilizing the emulsion,

X

I

Y --- C --- OH

Ic _{2 has an} alpha-hydroxy aliphatic acid structure wherein Y is hydroxy or COOH and X is (CH ₂ ) _n W where W is methyl or carboxyl and n is 0, 1 or 2.

Preferred alpha-hydroxy aliphatic acids are citric acid, lactic acid, malic acid, wherein the ratio of lactic acid to malic acid is preferably 5: 1 to 1: 1, more preferably 4: 1 to 1: 1. at least one alpha-hydroxy aliphatic acid is present in an amount of from 2 to 9% by weight, more preferably from 2 to 7% by weight.

After the alpha-hydroxy aliphatic acid has been added to the acidic emulsion, it can be partially neutralized so that the desired pH of the emulsion is safely achieved for greater functionality.

Phosphoric acid is one of the additional acids that helps protect the acid-sensitive surfaces that are cleaned with the emulsion cleaner of the present invention. Since it is a three-base acid, it must also be partially neutralized to obtain the pH of the emulsion in the desired range. For example, hydrogen phosphate, i.e. NaH ₂ PO ₄ or NH ₄ H ₂ PO _4, can be obtained by partial neutralization.

Phosphonic acid, one of the other two acids for protecting acid-sensitive surfaces from the solubilizing effect of the dicarboxylic acids of the concentrated emulsion of the present invention, is obviously only theoretically available, but its derivatives are stable and useful in the present invention. According to the present invention, phosphonic acid is understood to mean this. The structure of the phosphonic acid is as follows:

OH

I

Y --- P = 0

I OH wherein Y is a suitable substituent, preferably alkylamino or N-substituted alkylamino. Thus, for example, the preferred phosphonic acid component of the dense acidic emulsion of the present invention is aminotriomethylene phosphonic acid of the formula N (CH ₂ PH _X O ₃ ). Other useful phosphonic acids are ethylenediamine tetra-methylene-phosphonic acid, hexamethylenediamine-tetra-methylene-phosphonic acid and diethylenetriamine-penta- (methylene-phosphone) acid. These compounds are referred to as aminoalkylene phosphonic acids containing from 1 to 3 amino nitrogens, which also contain 3 or 4 lower alkylene phosphonic acid groups, wherein the lower alkylene group contains one or two carbon atoms and further contains C 0-22-6 alkylene- an alkylene group or groups which are present and are attached to the amino nitrogen when more than one such amino nitrogen is present in the aminoalkylene phosphonic acid molecule. It has been found that aminoalkylene phosphonic acids, which can also be partially neutralized at the desired pH of the microemulsion cleaner, have the desired stabilizing and protective activity in the cleaner, especially when present in combination with phosphate acid, to prevent alpha-hydroxyl aliphatic components from adversely affecting the cleaner. for European enamel surfaces.

The thickening agent optionally used in the acidic microemulsion is a xanthan gum called Kelzan T and marketed by Merek & Co. Xanthan gum is an extracellular heteropolysaccharide having a molecular weight of 1,000,000 to 10,000,000 and 0 to 10,000,000. 1% by weight, preferably 0.1-0.7% by weight, more preferably 0.2-0.6% by weight. When used at these concentration levels, the composition retains its microemulsion properties as long as the essential micellar aggregates are retained. The product is still sprayable and adheres well to a vertical wall. In addition, compositions containing xanthan gum can be easily removed from the surface to be cleaned without any particular mechanical action.

Therefore, these compositions have shear thinning properties. Other cellulose, hydroxypropyl cellulose, polyacrylamides, polyvinyl alcohol form shear thickening compositions.

Tap water may also be used in the microemulsions of the present invention, but low hardness water is preferred

use, hardness <150 ppm is generally preferred. THE tap water it is also possible to make suitable cleaners,

hardness not exceeding 3000 ppm. It is more advantageous to use distilled or deionized water with hardness!

content of ions less than 25 ppm.

Various other components may also be present in the purifiers of the present invention, including preservatives such as sodium benzoate, antioxidants or corrosion inhibitors, co-solvents, co-surfactants, polyvalent metal ions, fragrances, dyes, terpenes and terpincols, and various other conventionally liquid adjuvants and hard surface cleaners may also be present in detergents, provided that they do not interfere with the detergent and foam and limescale removal effects.

Of the various excipients that are not necessary for the production of a functional cleanser but may be desirable components, the most important are fragrances, which, with or without tarps, terpenes and hydrocarbons (which may or may not be added to fragrances), are particularly effective solvents for greasy surfaces, and in the oil-in-water type microemulsion form the dispersed phase.

Co-surfactants and polyvalent metal ions are also very important. The former can be used to stabilize the microemulsion, the latter to be added to improve the detergent effect, especially for thinner detergents, and when the polyvalent salts of the anionic detergent perform better as a detergent for cleaning greasy surfaces.

The various perfumes which are useful in forming the dispersed phase of the concentrated acidic microemulsion cleansers are those which are customary for use in detergents and are preferably present in liquid form. These include the esters, ethers, aldehydes, alcohols and alkanes used in perfumery, but most important are the essential oils, which have a very high terpene content. Thus, terpenes and terpineols appear to interact with the detergent components of the microemulsion, thereby improving the detergent effect. In addition, they form a stable dispersed phase of microemulsions. The present invention has found that, especially when using a resinous perfume, the dose of the comparatively expensive perfume can be reduced and compensated for with alpha terpineol, in some cases with other terpenes. For example, each 1% perfume can be replaced with 60-90%, such as 80% alpha-terpineol, to give the same resinous fragrance, with very good cleansing and microemulsion stability. Similarly, terpenes and other terpene-like substances can be used, but alpha-terpineol is preferred.

The polyvalent metal ions in the detergents of the present invention can be used in any suitable ion, including magnesium, usually preferred, and aluminum, copper, nickel, iron or calcium. The ion or mixture thereof may be added in a suitable form, in some cases as an oxide or hydroxide, but usually as a water-soluble salt. The polyvalent metal ion appears to react with the anion of the anionic detergent, either to replace the detergent cation or to form an equivalent solution in the emulsion. This improves the detergent effect and generally improves other properties of the product. If the polyvalent metal ion reacts with the detergent anion to form an insoluble product, then this polyvalent ion should be avoided. For example, calcium is reacted with a paraffin sulfonate anion to form an insoluble salt and, for example, calcium ions obtained from calcium chloride are omitted from the microemulsion cleaners of the invention containing a paraffin sulfonate detergent. Likewise, polyvalent ions or other components of the compositions of the present invention that react adversely with the other components are omitted. As mentioned above, the polyvalent metal ion is preferably magnesium and is added as the water-soluble salt to the other emulsion components. For example, magnesium sulfate is preferred, usually in the form of heptahydrate (as the Epson salt), but other hydrates or anhydride may also be used. In general, sulfates of polyvalent metals are used because the sulfate anion is also the anion of other anionic detergents and, for some of these detergents, it is formed as a by-product of neutralization.

The co-surfactant components of acidic detergents reduce surface tension or surface tension, between lipophilic droplets and between continuous aqueous media up to 10 ~ ³ dynes / cm. As a result, the dispersed phase spheres disintegrate spontaneously until they are small enough to become invisible to the human eye, thus forming a pure microemulsion. In such a microemulsion, the surface area of the dispersed phase is greatly increased, thereby increasing its solubility and low degreasing capacity, so that the acidic microemulsion is significantly more effective as a detergent for removing greasy impurities than conventional emulsion sized dispersed wood.

- 19 zis globules. Among the co-surfactants, water-soluble lower alkanols (sometimes containing 3 or 4 carbon atoms) containing from 2 to 4 carbon atoms per molecule may be used in the purifiers of the present invention.

Polypropylene glycols containing from 2 to 18 propoxy units; and

Monoalkyl lower glycol ethers of the formula RO (X) _n H wherein R is C 1 -C 4 alkyl, X is CH ₂ CH ₂ CH ₂ O, or CH (CH 3) CH ₂ O, and n is 1 to 4; and aryl-substituted C 1 -C 4 alkanols, propylene carbonate; C2-C6 hydroxyaliphatic acids, such as mono-, di-, and trihydroxy-substituted aliphatic mono-, di-, and tricarboxylic acids having 2 to 6 carbon atoms; and mono-, di- and triesters of lower alkyl phosphoric acid, wherein the lower alkyl group has from 1 to 4 carbon atoms, and mixtures thereof.

It will be appreciated that other co-surfactants as defined above may be used in combination with alpha-hydroxyaliphatic acids which act as co-surfactants. These non-acidic co-surfactants may be used in combination with alpha-hydroxy aliphatic acid co-surfactants in an amount of 0.1 to 5% by weight, preferably 0.5 to 4% by weight, depending on the concentration of the alpha-hydroxy aliphatic co-surfactant.

Examples of such co-surfactants are lactic, malic, citric, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, which are most effective.

It is apparent from the list of useful co-surfactants that the cleaning agents of the present invention use malic acid, lactic acid and citric acid, and a mixture of these components is very useful in lowering the pH of the product so as to remove the soap foam. , limescale on the surface to be cleaned and at the same time act as a co-surfactant, thereby improving the appearance of the product and making the removal of grease from such surfaces more efficient. A similar double effect can be obtained by using other specified acidic substances which are co-surfactants in the above cleaners.

It is important for the detergents of the present invention to keep the proportion of the components within a certain range so that the product is most effective in removing greasy dirt and limescale, soap foam and other debris from hard surfaces that are being treated and thus such treatment. we can protect these surfaces.

Preferably, the detergent is present in a detergent ratio sufficient to remove greasy and oily impurities; the ratio of alpha-hydroxy aliphatic acid or acids should be such that we can remove the soap foam and scale, the amount of phosphonic acid or phosphoric acid or phosphonic acid mixture should be sufficient to protect the acid-sensitive surfaces of the alpha-hydroxy aliphatic acid acids, and the aqueous medium is preferably a solvent or suspending agent for the desired components and any excipients may be present. Typically, the percent composition of the components is 0-1% xanthan gum, 1-9% synthetic anionic organic detergent, 0-5% synthetic organic nonionic detergent, 2-9% alpha-hydroxy aliphatic acid,

0.05-0.6% phosphoric acid or mono-salt thereof; 0.005-2% phosphonic acid or acids; 0-0.6% aminoalkylene phosphonic acid or acids or monophosphonic salts thereof. Any remaining water or excipient, if present.

Among the alpha-hydroxy aliphatic acids, a mixture of lactic acid and malic acid is preferred.

The ratio of alpha-hydroxy aliphatic acid to aminoalkylene phosphonic acid in the composition according to the invention is 5: 1250: 1, preferably 2: 1 to 10: 1, and the ratio of alpha-hydroxy aliphatic acid to phosphoric acid is 5: 2 to 25: 1. .

The cleaning agent of the present invention will usually contain from 0.1 to 3% polyvalent ions, preferably magnesium or aluminum, more preferably magnesium, especially when anionic surfactant is present. The percentage of perfume is usually from 0.2 to 2%, preferably from 0.5 to 1.5%, of which at least 0.1% is terpene or terpineol. Terpineol is alpha-terpineol and is preferably added to the composition to reduce the amount of perfume while the total amount of perfume including alpha terpineol is 50-90% terpineol, preferably 80%.

The pH of the various preferred microemulsion cleaners is usually 1 to 4, preferably 1.5 to 3.5, especially 3. The water content of the microemulsion is usually 75 to 90, preferably 80 to 85%, and the excipient content is 0 to 5%, usually 1 to 5%. 3%. If the pH is not within the desired range, it is usually adjusted by the addition of sodium hydroxide or a suitable acid, for example sulfuric acid, but usually the pH is raised rather than lowered and, if lowered, * * · alpha-hydroxy acid using a mixture.

Liquid cleansers are prepared by mixing the various components, the order or addition being not critical. However, it is desirable for xanthan gum, if desired, to be first mixed with water. The various water soluble components are mixed and introduced into the xanthan gum solution, the oil soluble components are mixed together in a separate operation and the two mixtures are mixed. The oil-soluble portion is added to the water-soluble portion in water with stirring.

In some cases, the process may be modified to prevent undesirable reactions between the components. For example, concentrated phosphoric acid is not added directly to magnesium sulfate or to a dye, but is added in aqueous solution, preferably at dilution of the components.

The detergent is conveniently packaged in a manually operated spray dispenser container, which is usually and preferably made of a synthetic organic polymeric plastic such as polyethylene, polypropylene or polyvinyl chloride. Such a container is preferably nylon or other non-reactive plastic closure, spray nozzle, dip tube and associated dispensing parts, and the resulting packaged cleaner is ideal for spraying and wiping applications. However, in some cases, when scale deposits of soapstone and soap are large enough, we may leave the detergent until it dissolves or loosens and can then be wiped or rinsed or * ·· ·

- 23 can be applied multiple times and removed several times until the deposits disappear.

The following examples illustrate further details of the invention. The parts, portions and percentages in the examples are in weight and the temperature is in ° C.

Example 1

Component weight%

THE B C Sodium laureth sulfate 4.00 3.0 4.0 C13-C15 sodium benzoate 0.30 0.3 0.3 Magnesium sulphate heptahydrate 1.50 1.5 1.5 Malic acid 2.0 2.0 - Milk 2.0 3.0 - Citric acid - - 4.0 Aminotri- 0.25 0.25 0.25 methylphosphonic acid phosphoric acid 0,425 0,425 0,425 Perfume (40% terpene- 0.8 0.8 0.8 content) Paint 0,002 0,002 0,002 Water the rest the rest the rest PH 3.0 3.0 3.0 Brookfield viscosity 10 10 10

room temperature, # 2 spindle

Sorbins (cps) residual

100.00 • ·· *>

• · · · 9 • · * * 4 Λ · · · · · ··· · ««

- 24 The microemulsion cleaner is prepared by dissolving the xanthan gum and benzoates, if desired, and then dissolving the detergent in water, then adding the remainder of the water soluble substance to the detergent solution with the exception of perfume and adjusting agent, sodium hydroxide. hydroxide solution. The pH is adjusted to 3 and the perfume is mixed with the aqueous solution to give the desired microemulsion which is pure blue.

The acidic detergent is packaged in polyethylene pressurized bottles equipped with a polypropylene spray nozzle that can be set to a closed, spray and flow position. During use, the microemulsion is sprayed into the bathtub onto the bathtub ring, which also contains limescale, in addition to soap foam and greasy dirt. Apply 5 ml to a 5 m ring, about 3 cm wide. After application and waiting, which is about 2 minutes, the ring is wiped off with a sponge, rinsed with water and found to have effectively removed greasy dirt, soap foam and even limescale. In cases where the scale is particularly thick or sticky, a second application may be desirable, but this is considered normal. The surface of the tub can be rinsed as it is very easy to rinse the tub or ink, but this rinse is not necessary. Sometimes dry wiping is enough, but if you want to remove any acidic residue from the surface, you can wipe the surface with a sponge or wipe it with a damp cloth, but in that case you do not need to use more than the cleaning agent used. ·· · · * · ten times the weight of ♦ Ο ··· ·· ♦. In other words, the surface does not need to be rinsed thoroughly with water, it will still be clean and shiny, provided it was originally shiny. For other applications of detergent, it can be used to clean shower tiles, bathroom floor tiles, kitchen tiles, sinks and enamel, usually without damaging the surface. Many of these surfaces are acid resistant, but commercially available products should not damage less resistant surfaces, such as European enamel (often for cast iron or sheet steel based materials, these are called zirconium white powder enamels). The detergent according to the invention effectively cleans hard surfaces, contains ionizable acids and is therefore not suitable for use on acid-sensitive surfaces. However, it has been found that the white enamel bathtubs are not harmed by the exemplary formulation, these bathtubs are severely affected by the formulations which are exactly exemplified, except that they do not contain a phosphonic acid or a mixture of phosphorus phosphonic acid.

Claims (8)

Patent claims An acidic microemulsion composition for baths and other hard surface articles which are acid resistant, such as white zirconium enamel, having a pH of from 1 to 4 and which removes limescale, soap foam and greasy dirt from such surfaces without damaging it. these surfaces being characterized by the presence of synthetic organic detergents, alpha-hydroxy aliphatic acid, aminoalkylene phosphonic acid, water, and perfume to remove grease dirt from the surfaces. Composition according to claim 1, characterized in that the alpha-hydroxy aliphatic acid has from 2 to 6 carbon atoms, the aminoalkylene phosphonic acid has from 1 to 2 carbon atoms. 3 amino nitrogen, 3 or Contains 4 lower alkylene phosphonic acids, lower alkylene groups having 0-2.2-6 carbon atoms, where alkylene or alkylenes are present and linking or linking the amino nitrogen when more nitrogen is present in the aminoalkylene phosphonic acid. Third THE The composition of claim 2, a z z a 1 signal 1 e m e alpha-hydroxy aliphatic acid and the amino alkylene- ratio of phosphonic acid to 5: 1 to 250: 1. 4. THE The composition of claim 3, a z z a 1 characterized in that the synthetic organic detergent 8 C 18 alkyl sulfate. The composition of claim 1, wherein a phosphoric acid is present which enhances the effect of aminoalkylene phosphonic acid on protecting zirconium white enamel surfaces to be purified from alpha-hydroxy aliphatic acids and wherein the ratio of phosphoric acid to aminoalkylene phosphonic acid is 2: 1 to 10: 1, and wherein the ratio of alpha-hydroxy aliphatic acid to phosphoric acid is 5: 2 to 25: 1. 6. That 5th Composition according to Claim 1, characterized in that 1-9% synthetic organic anionic detergent, 1-6% synthetic organic anionic detergent, It contains 2 to 9% alpha-hydroxy aliphatic acid, 0.05 to 1% phosphoric acid and 0.01 to 0.3% aminoalkylene phosphonic acid. 7. A composition according to claim 1 wherein the alpha-hydroxy aliphatic acid is a mixture of malic and lactic acid. 8. The composition of claim 1 wherein the alpha-hydroxy aliphatic acid is citric acid.